KR101734165B1 - Poly(arylene ether)/polyamide compositions, methods, and articles - Google Patents

Abstract

The thermoplastic compositions of the present invention comprise a specified amount of polyamide, poly (arylene ether) -polysiloxane block copolymer and metal dialkyl phosphinate. The composition exhibits excellent flame retardancy without exhibiting ductility deterioration normally observed in other flame retardant polyamide-poly (arylene ether) compositions. Also disclosed is a method of forming the composition. The composition is useful for the molding of electrical and automotive parts.

Description

POLYAMIDE ARYLENE ETHER / POLYAMIDE COMPOSITIONS, METHODS, AND ARTICLES Technical Field The present invention relates to poly (arylene ether) / polyamide compositions,

The present invention relates to poly (arylene ether) / polyamide compositions, methods and articles.

Poly (arylene ether) resins have been blended with polyamide resins to provide compositions having a wide variety of beneficial properties, such as heat resistance, chemical resistance, impact strength, hydrolytic stability and dimensional stability.

In some applications it is preferred to use poly (arylene ether) / polyamide blends with excellent flame retardancy. Unfortunately, such flame retardancy is difficult to achieve for articles having thin sections while maintaining or improving mechanical properties. Conventional flame retardant poly (arylene ether) / polyamide blends often use silicone fluids and boron phosphate to achieve good flame retardancy grades, but the use of these flame retardants is associated with a loss of ductility. It is also particularly difficult to achieve flame retardancy in glass fiber reinforced thermoplastic compositions because the presence of a reinforcing filler alters the mode of combustion of the composition relative to the non-reinforcing composition. There remains a need for poly (arylene ether) / polyamide compositions that exhibit excellent flame retardancy while at least yielding or even improving ductility.

One embodiment of the present invention comprises about 55 to about 95 weight percent of a blended blend of polyamide and poly (arylene ether) -polysiloxane block copolymer; And about 1 to about 12 weight percent metal dialkylphosphinate, all of the weight percentages being based on the total weight of the composition.

Another embodiment provides a composition comprising about 22 to about 85 weight percent polyamide, about 6 to about 57 weight percent poly (arylene ether) -polysiloxane block copolymer, and about 1 to about 12 weight percent metal dialkyl phosphine (All percentages by weight being based on the total weight of the composition) consisting of forming the composition by melt blending the nate.

These and other embodiments, including articles comprising the composition, are described in detail below.

1 is a scanning electron microscope photograph of the composition of Comparative Example 1. Fig.
Fig. 2 is a scanning electron micrograph of the composition of Comparative Example 2. Fig.
3 is a scanning electron microscope photograph of the composition of Comparative Example 5. Fig.
Figure 4 is a scanning electron micrograph of Example 3 composition.
5 is a scanning electron micrograph of the composition of Comparative Example 6. Fig.
6 is a scanning electron microscopic photograph of the composition of Comparative Example 7;

The inventors of the present invention have found that the addition of poly (arylene ether) -polysiloxane block copolymer significantly improves the effect of metal dialkyl phosphinates in improving the flame retardancy of polyamide compositions. Thus, one embodiment comprises about 55 to about 95 weight percent of a blended blend of a polyamide and a poly (arylene ether) -polysiloxane block copolymer; And from about 1 to about 12 weight percent of a metal dialkyl phosphinate, all percentages by weight being based on the total weight of the composition.

Polyamides are used to prepare the commercialized blends. Polyamides, also known as nylons, are characterized by the presence of a plurality of amide (-C (O) NH-) groups and are disclosed in U.S. Patent 4,970,272 to Gallucci. Suitable polyamide resins include polyamide-6, polyamide-6,6, polyamide-4, polyamide-4,6, polyamide-12, polyamide-6,10, polyamide- 6,12, amorphous polyamide, polyamide 6 / 6T and polyamide 6,6 / 6T (with less than 0.5% by weight of triamine), polyamide 9T and combinations thereof. In some embodiments, the polyamide resin is comprised of polyamide-6,6. In some embodiments, the polyamide resin is comprised of polyamide-6 and polyamide-6,6. In some embodiments, the combination of polyamide resin or polyamide resin has a melting point (T _m ) of 171 ° C or higher. When the polyamide is composed of a super tough polyamide, i.e., a rubber-reinforced polyamide, the composition may or may not include a separate impact modifier.

Polyamide resins can be prepared by a number of well known methods, such as those described in U.S. Patent Nos. 2,071,250, 2,071,251, 2,130,523, and 2,130,948 to Carothers; 2,241,322 and 2,312,966 for Hanford; And Bolton et al., ≪ RTI ID = 0.0 > 2,512,606. ≪ / RTI > Polyamide resins are commercially available from a variety of sources.

An intrinsic viscosity of 400 milliliters (mL / g) or less per gram, more specifically a viscosity of 90 to 350 mL / g, more particularly 110 to 350 mL / g, as measured in a 0.5 weight percent solution in 96 wt.% Sulfuric acid according to ISO 307, To 240 mL / g may be used. The polyamide may have a relative viscosity of 6 or less, more specifically a relative viscosity of 1.89 to 5.43, even more specifically a relative viscosity of 2.16 to 3.93. The relative viscosity is determined according to DIN 53727 in a 1 wt% solution in 96 wt% sulfuric acid.

In one embodiment, the polyamide resin is composed of a polyamide having an amine end group concentration of 35 microequivalents (μeq / g) or more per gram of polyamide determined by titration with HCl. The amine end group concentration may be at least 40 μeq / g, more specifically at least 45 μeq / g. The amine end group content can be determined by dissolving the polyamide in a suitable solvent, optionally with heating. The polyamide solution is titrated with a 0.01 normal hydrochloric acid (HCl) solution using an appropriate labeling method. The amount of amine end groups is calculated based on the volume of the HCl solution added to the sample, the volume of HCl used as a blank, the molar concentration of the HCl solution, and the weight of the polyamide sample.

Poly (arylene ether) -polysiloxane block copolymers are used to make the commercialized blends. As used herein, the term "poly (arylene ether) -polysiloxane block copolymer" refers to a block copolymer composed of at least one poly (arylene ether) block and at least one polysiloxane block.

In some embodiments, the poly (arylene ether) -polysiloxane block copolymer is prepared by an oxidation copolymerization process. In this method, the poly (arylene ether) -polysiloxane block copolymer is the product of a process comprising oxidation-copolymerizing a monomer mixture consisting of a monohydric phenol and a hydroxyaryl-terminated polysiloxane. This synthetic approach is best for making block copolymers having a relatively low polysiloxane content. Thus, in some embodiments, the monomer mixture comprises about 90 to about 99 parts by weight of a monohydric phenol and about 1 to about 10 parts by weight of a hydroxyaryl-terminated polyol, based on the total weight of the monohydric phenol and the hydroxyaryl-terminated polysiloxane, Polysiloxane. Hydroxyaryl-diterminated polysiloxanes comprise a plurality of repeating units having the structure:

(Wherein each R ⁷ is independently hydrogen, C ₁ -C ₁₂ hydrocarbyl or halo-C ₁ -C ₁₂ hydrocarbyl bilim); And two terminal units having the following structure:

C ₁ -C ₁₂ hydrocarbyl, C ₁ -C ₁₂ hydrocarbyloxy, or halogen, each of R ⁸ is independently hydrogen, C ₁ -C ₁₂ hydrocarbyl or C ₁ -C ₁₂ hydrocarbyl, halo-C ₁₂ hydrocarbyl bilim).

In some embodiments, the monovalent phenol is comprised of 2,6-dimethylphenol, and the hydroxyaryl-terminated polysiloxane has the structure:

Wherein n ranges from about 5 to about 100 on average.

Oxidation polymerization of a mixture of monohydric phenol and hydroxyaryl-terminated polysiloxane results in poly (arylene ether) -polysiloxane block copolymer as the desired product and poly (arylene ether) (without incorporated polysiloxane block) as byproduct . It is not necessary to separate the poly (arylene ether) from the poly (arylene ether) -polysiloxane block copolymer. Thus, the poly (arylene ether) -polysiloxane block copolymer may be included in the composition of the present invention as a "reaction product" comprising both poly (arylene ether) and poly (arylene ether) -polysiloxane block copolymers. Certain separation procedures, such as precipitation from isopropanol, can confirm that the reaction product is essentially free of residual hydroxyaryl-terminated polysiloxane starting material. In other words, this separation procedure ensures that the polysiloxane content of the reaction product is essentially all of the poly (arylene ether) -polysiloxane block copolymer.

In some embodiments, the poly (arylene ether) -polysiloxane block copolymer is a poly (arylene ether) -polysiloxane block copolymer reaction comprising a poly (arylene ether) and a poly (arylene ether) -polysiloxane block copolymer It is provided in the form of product. The poly (arylene ether) -polysiloxane block copolymer may be comprised of a polysiloxane block consisting of a poly (arylene ether) block, and an average of about 35 to about 80 siloxane repeat units. The poly (arylene ether) -polysiloxane block copolymer reaction product may comprise about 1 to about 8 weight percent siloxane repeat units and 92 to 99 weight percent arylene ether repeat units. The poly (arylene ether) -polysiloxane block copolymer reaction product may have a weight average molecular weight of at least 30,000 atomic mass units.

When the poly (arylene ether) -polysiloxane block copolymer is provided in the form of a poly (arylene ether) -polysiloxane block copolymer reaction product, the reaction product is composed of poly (arylene ether). The poly (arylene ether) is a polymerization product of monovalent phenol alone and is a by-product of the synthesis of block copolymers. When the monohydric phenol is composed of a single compound (for example 2,6-dimethylphenol), the poly (arylene ether) is a homopolymerized product of the single monohydric phenol. When the monovalent phenol is composed of two or more distinct monovalent phenol species (for example, a mixture of 2,6-dimethylphenol and 2,3,6-trimethylphenol), the poly (arylene ether) Or more of the above-mentioned monovalent phenol species. It was not possible to assign an arylene ether residue between the poly (arylene ether) and the poly (arylene ether) -polysiloxane block copolymer when the nuclear magnetic resonance method described in the working examples was used. However, the presence of a poly (arylene ether) can be avoided in such isolated products as "tail" groups as defined below (for example, 2,6-dimethylphenol when the monovalent phenol is 2,6- (E.g., 3,3 ', 5,5'-tetramethyl-4,4'-biphenol) as defined below, and / . ≪ / RTI >

When the poly (arylene ether) -polysiloxane block copolymer is provided in the form of a poly (arylene ether) -polysiloxane block copolymer reaction product, it is comprised of a poly (arylene ether) -polysiloxane block copolymer. The poly (arylene ether) -polysiloxane block copolymer is comprised of a poly (arylene ether) block and a polysiloxane block. The poly (arylene ether) block is a residue obtained by polymerizing monovalent phenol. In some embodiments, the poly (arylene ether) block is comprised of an arylene ether repeat unit having the structure:

For each repeating unit in the above formula, each Z < ^{1 >} Is independently selected from the group consisting of halogen, unsubstituted or substituted C ₁ -C ₁₂ hydrocarbyl (when the hydrocarbyl group is not a tertiary hydrocarbyl), C ₁ -C ₁₂ hydrocarbylthio, C ₁ -C ₁₂ hydrocarbyl Carboyloxy, or C ₂ -C ₁₂ halohydrocarbyloxy (at least two carbon atoms separate the halogen and oxygen atoms); Each Z ² is independently selected from the group consisting of hydrogen, halogen, unsubstituted or substituted C ₁ -C ₁₂ hydrocarbyl (when the hydrocarbyl group is not a tertiary hydrocarbyl), C ₁ -C ₁₂ hydrocarbylthio, C ₁ -C ₁₂ hydrocarbyloxy, or C ₂ -C ₁₂ halohydrocarbyloxy (at least two carbon atoms separate the halogen and oxygen atoms). The term " hydrocarbyl "as used herein refers to a moiety that is used as such, or as part of a prefix, suffix or other term, or contains only carbon and hydrogen. The moiety may be aliphatic or aromatic, linear, cyclic, bicyclic, branched, saturated or unsaturated. It may also contain a combination of aliphatic, aromatic, straight chain, cyclic, bicyclic, branched, saturated and unsaturated hydrocarbon moieties. When said hydrocarbyl moiety is described as substituted, it may optionally contain heteroatoms above the carbon and hydrogen member of said substituted moiety. Thus, when described as specifically substituted, the hydrocarbyl moieties may also be composed of one or more substituents such as halogen (including fluorine, chlorine, bromine and iodine), carboxylic acid groups, amino groups, hydroxyl groups, Or a divalent heteroatom-containing group such as an oxygen atom, a silicon atom, and a carbonyl group in the backbone of the hydrocarbyl moiety. In some embodiments, the poly (arylene ether) block comprises 2,6-dimethyl-1,4-phenylene ether repeating units, that is, repeating units having the following structure:

Or 2,3,6-trimethyl-1,4-phenylene ether repeating unit, or a combination thereof.

The polysiloxane block is a residue of a hydroxyaryl-terminated polysiloxane. In some embodiments, the polysiloxane block is composed of repeating units having the structure:

(Wherein each R ⁷ is independently hydrogen, C ₁ -C ₁₂ hydrocarbyl or halo-C ₁ -C ₁₂ hydrocarbyl bilim); The polysiloxane block is further comprised of end units having the following structure:

C ₁ -C ₁₂ hydrocarbyl, C ₁ -C ₁₂ hydrocarbyloxy, or halogen, each of R ⁸ is independently hydrogen, C ₁ -C ₁₂ hydrocarbyl or C ₁ -C ₁₂ hydrocarbyl, halo-C ₁₂ hydrocarbyl bilim). In some embodiments, each R ⁸ is independently C ₁ -C ₆ alkyl, specifically C ₁ -C ₃ alkyl, more particularly methyl. In some embodiments, the polysiloxane repeat unit is comprised of dimethylsiloxane (-Si (CH ₃ ) ₂ O-) units. In some embodiments, the polysiloxane block has the following structure:

Wherein n is from 35 to 60.

In some embodiments, the poly (arylene ether) block is comprised of an arylene ether repeat unit having the structure:

The polysiloxane block has the following structure:

Wherein n is from 35 to 60; The poly (arylene ether) -polysiloxane block copolymer reaction product has a number average molecular weight of 10,000 to 30,000 atomic mass units.

The hydroxyaryl-terminated polysiloxane is composed of at least one hydroxyaryl end group. In some embodiments, the hydroxyaryl-terminated polysiloxane has a single hydroxyaryl end group, in which case a poly (arylene ether) -polysiloxane diblock copolymer is formed. In another embodiment, the hydroxyaryl-terminated polysiloxane has two hydroxyaryl end groups, in which case a poly (arylene ether) -polysiloxane diblock and / or triblock copolymer is formed. It is also possible that the hydroxyaryl-terminated polysiloxane has a branched structure to allow at least three hydroxyaryl end groups and to form the corresponding branched copolymer.

As noted above, the polysiloxane block may comprise an average of about 35 to about 80 siloxane repeat units. Within this range, the number of siloxane repeat units can be from about 35 to about 60, more specifically from about 40 to about 50. The number of siloxane repeat units in the polysiloxane block is essentially unaffected by the copolymerization and separation conditions and is thus equal to the number of siloxane repeat units in the hydroxyaryl-terminated polysiloxane starting material. Unless otherwise known, the average number of siloxane repeat units per hydroxyaryl-terminated polysiloxane molecule can be determined by an NMR method that compares the signal intensity associated with the siloxane repeat unit to the signal intensity associated with the hydroxyaryl end group. For example, when the hydroxyaryl-terminated polysiloxane is eugenol-capped polydimethylsiloxane, the proton nuclear magnetic resonance ( ¹ H NMR) method (the proton of dimethylsiloxane resonance and the proton of eugenol methoxy group Lt; / RTI > are compared) to determine the average number of siloxane repeat units.

(Arylene ether) -polysiloxane block copolymer reaction product, when prepared by the oxidation copolymerization process, is present in the poly (arylene ether) -polysiloxane block copolymer reaction product in an amount of from about 1 to about 8 weight percent % Of siloxane repeating units and 92 to 99 wt% of arylene ether repeating units. Within this range, the weight percent of siloxane repeat units can be from about 3 to about 7 weight percent, specifically from about 4 to about 6 weight percent, more specifically from about 4 to about 5 weight percent; The weight percent of arylene ether repeat units can be from about 93 to about 97 weight percent, specifically from about 94 to about 96 weight percent, and more specifically from about 95 to about 96 weight percent.

When prepared by the oxidation copolymerization process, the poly (arylene ether) -polysiloxane block copolymer reaction product may have a weight average molecular weight of at least about 30,000 atomic mass units. In some embodiments, the weight average molecular weight is in the range of from about 30,000 to about 150,000 atomic mass units, specifically from about 35,000 to about 120,000 atomic mass units, more specifically from about 40,000 to about 90,000 atomic mass units, About 70,000 atomic mass units. In some embodiments, the poly (arylene ether) -polysiloxane block copolymer reaction product comprises about 10,000 to about 50,000 atomic mass units, specifically about 10,000 to about 30,000 atomic mass units, and more specifically about 14,000 to about 24,000 atoms And has a number average molecular weight in mass units. Detailed chromatographic methods for determining molecular weight are described in the Examples below.

When prepared by the oxidation copolymerization process, the poly (arylene ether) -polysiloxane block copolymer reaction product may comprise relatively small amounts of very low molecular weight species. Thus, in some embodiments, the poly (arylene ether) -polysiloxane block copolymer reaction product comprises less than 25% by weight of molecules having a molecular weight of less than 10,000 atomic mass units, specifically less than 5 atomic mass units of less than 10,000 atomic mass units To 25% by weight of molecules, more specifically from 7 to 21% by weight of molecules having a molecular weight of less than 10,000 atomic mass units. In some embodiments, the molecule having a molecular weight of less than 10,000 atomic mass units is comprised of an average of 5 to 10 weight percent siloxane repeat units, specifically 6 to 9 weight percent siloxane repeat units.

Likewise, the poly (arylene ether) -polysiloxane block copolymer reaction product may also comprise relatively small amounts of very high molecular weight species. Thus, in some embodiments, the poly (arylene ether) -polysiloxane block copolymer reaction product comprises less than 25% by weight of molecules having a molecular weight greater than 100,000 atomic mass units, specifically 5 To 25% by weight of molecules, more specifically from 7 to 23% by weight of molecules having a molecular weight greater than 100,000 atomic mass units. In some embodiments, a molecule having a molecular weight greater than 100,000 atomic mass units is comprised of an average of 3 to 6 weight percent siloxane repeat units, specifically 4 to 5 weight percent siloxane repeat units.

In some embodiments, the poly (arylene ether) -polysiloxane block copolymer reaction product has an intrinsic viscosity of at least about 0.3 deciliters per gram as measured in chloroform at 25 占 폚. The intrinsic viscosity is from about 0.3 to about 0.6 deciliter per gram, specifically from about 0.3 to about 0.5 deciliter per gram, more specifically from about 0.31 to about 0.55 deciliter per gram, even more specifically from about 0.35 to about 0.5 gram per gram Can be 0.47 deciliter.

One such indication of the efficiency with which the oxidation copolymerization process binds the hydroxyaryl-terminated polysiloxane into the block copolymer is a low concentration of the so-called poly (arylene ether) "tail" group. In the single-polymerization of 2,6-dimethylphenol, a large fraction of the product molecules is obtained in such a way that the linear product molecules terminate in the 3,5-dimethyl-4-hydroxyphenyl "head" Called head-to-tail structure ending with a 6-dimethylphenoxy "tail ". Thus, when the monohydric phenol is composed of 2,6-dimethylphenol, the poly (arylene ether) tail has the following structure:

Wherein the 3-, 4- and 5- positions of the ring are substituted with a hydrogen atom (i.e., 2,6-dimethylphenoxy does not include a divalent 2,6-dimethyl-1,4-phenylene ether group). In copolymerizing the monohydric phenol with the hydroxyaryl-terminated polysiloxane, the conjugation of the hydroxyaryl-terminated polysiloxane into the block copolymer will reduce the concentration of the arylene ether "tail" group. When the monohydric phenol is composed of 2,6-dimethylphenol, especially when the poly (arylene ether) -polysiloxane block copolymer reaction product is the sole source of the arylene ether unit in the composition, Based on the weight, of a 2,6-dimethylphenoxy group of 0.4% by weight or less, specifically 0.2 to 0.4% by weight. When the monohydric phenol is composed of 2,6-dimethylphenol, especially when the composition is composed of poly (arylene ether) in addition to being present in the poly (arylene ether) -polysiloxane block copolymer reaction product, The composition may comprise up to 1% by weight, specifically from 0.2 to 1% by weight, based on the weight of the composition, of a 2,6-dimethylphenoxy group.

The poly (arylene ether) -polysiloxane block copolymer reaction product may also include groups derived from diphenoquinone, the oxidation product of the monohydric phenol. For example, if the monovalent phenol is 2,6-dimethylphenol, the reaction product of the poly (arylene ether) -polysiloxane block copolymer may comprise from 1.1 to 2.0 wt% 2,6-dimethyl-4- (3, 5-dimethyl-4-hydroxyphenyl) phenoxy group.

The poly (arylene ether) -polysiloxane block copolymer reaction product can be separated from the solution by a separation procedure that minimizes both volatile and non-volatile contaminants. For example, in some embodiments, the poly (arylene ether) -polysiloxane block copolymer reaction product comprises less than 1% by weight of total volatiles, specifically 0.2 to 1% by weight of total volatiles, Lt; RTI ID = 0.0 > example. ≪ / RTI > In some embodiments, the monomer mixture is oxidatively copolymerized in the presence of a catalyst consisting of a metal (e.g., copper or manganese) and the poly (arylene ether) -polysiloxane block copolymer reaction product is 100 parts by weight specifically from 0.5 to 100 million parts by weight of the metal, more specifically from 10 to 50 million parts by weight of the metal, even more specifically from 20 to 50 million parts by weight of the metal.

Wherein the poly (arylene ether) -polysiloxane block copolymer reaction product is formed by oxidation-copolymerizing the monohydric phenol with the hydroxyaryl-terminated polysiloxane to form a poly (arylene ether) -polysiloxane block copolymer reaction product ≪ / RTI > The oxidation copolymerization may be initiated in the presence of at least 50 weight percent hydroxyaryl-terminated polysiloxane and up to 50 weight percent monovalent phenol. In some embodiments, the oxidation copolymerization comprises at least 80 weight percent hydroxyaryl-terminated polysiloxane, specifically at least 90 weight percent hydroxyaryl-terminated polysiloxane, more specifically 100 weight percent hydroxyaryl-terminated polysiloxane Lt; / RTI >

The hydroxyaryl-terminated polysiloxane may be composed of siloxane repeat units having an average of from about 35 to about 80. In some embodiments, the hydroxyaryl-terminated polysiloxane has an average of from about 40 to about 70 siloxane repeat units, specifically from about 40 to about 60 siloxane repeat units, and more specifically from about 40 to about 50 siloxane repeat units . The hydroxyaryl-terminated polysiloxane may comprise from about 1 to about 8 weight percent, specifically from about 3 to about 8 weight percent, of the combined weight of the monohydric phenol and the hydroxyaryl-terminated polysiloxane.

The oxidation copolymerization may be performed at a reaction time of 110 minutes or more. The reaction time is the time elapsed between the onset and the termination of the oxygen flow (for convenience, the description herein refers to "oxygen" or "oxygen flow" repeatedly, but including air, any oxygen- May be used as an oxygen source). In some embodiments, the reaction time is 110 to 300 minutes, specifically 140 to 250 minutes, more specifically 170 to 220 minutes.

The oxidation copolymerization may include a "build time" which is the time between completion of monomer addition and termination of the oxygen flow. In some embodiments, the reaction time is comprised of a build time of 80 to 160 minutes. In some embodiments, the reaction temperature during at least a portion of the build time can be 40 to 60 占 폚, specifically 45 to 55 占 폚.

After completion of the copolymerization reaction, the poly (arylene ether) -polysiloxane block copolymer reaction product can be separated from the solution using methods known in the art for separating the poly (arylene ether) from the solution. For example, the poly (arylene ether) -polysiloxane block copolymer reaction product may be separated by precipitation with an antisolvent such as a C ₁ -C ₆ alkanol comprising methanol, ethanol, n-propanol and isopropanol . The inventors of the present invention have observed that the use of isopropanol is advantageous because isopropanol is a good solvent for the unreacted hydroxyaryl-terminated polysiloxane. Thus, precipitation and washing with isopropanol substantially removes the hydroxyaryl-terminated polysiloxane from the separated product. As an alternative to precipitation, the poly (arylene ether) -polysiloxane block copolymer reaction product can be separated by a direct separation method involving devolatilizing extrusion. In some embodiments, the composition comprises less than or equal to 1.5 wt% hydroxyaryl-terminated polysiloxane, specifically less than or equal to 0.5 wt% hydroxyaryl-terminated polysiloxane, based on the total weight of the composition. The precipitation of the poly (arylene ether) -polysiloxane block copolymer reaction product in isopropanol was observed to be effective in separating the hydroxyaryl-terminated polysiloxane from the reaction product.

In some embodiments, the poly (arylene ether) -polysiloxane block copolymer reaction product binds a hydroxyaryl-terminated polysiloxane starting material in weight percent greater than 75 into the poly (arylene ether) -polysiloxane block copolymer . Specifically, the amount of hydroxyaryl-terminated polysiloxane incorporated into the poly (arylene ether) -polysiloxane block copolymer is at least 80% by weight, more particularly at least 85% by weight, more particularly at least 90% by weight %, Even more specifically at least 95% by weight.

In a very specific process for preparing the poly (arylene ether) -polysiloxane block copolymer reaction product, the monovalent phenol is 2,6-dimethylphenol; The hydroxyaryl-terminated polysiloxane is a eugenol-capped polydimethylsiloxane composed of 35 to 60 dimethylsiloxane units; Wherein the oxidation copolymerization is initiated in the presence of at least 90 wt% hydroxyaryl-terminated polysiloxane and 2 to 20 wt% monovalent phenol; The oxidation copolymerization is carried out at a reaction time of from 170 to 220 minutes; The hydroxyaryl-terminated polysiloxane constitutes from 2 to 7% by weight of the combined weight of the monohydric phenol and the capped polysiloxane.

Additional details regarding the preparation, characterization and characterization of the poly (arylene ether) -polysiloxane block copolymer reaction product can be found in co-pending U.S. patent application 12 / 277,835, filed November 25, 2008.

In addition to the oxidation copolymerization processes described above, polyesterisation methods can be used to form poly (arylene ether) -polysiloxane block copolymers. When a polyesterization process is used, the product is a multi-block copolymer consisting of at least two poly (arylene ether) blocks and at least two polysiloxane blocks. Thus, in some embodiments, the poly (arylene ether) -polysiloxane block copolymer is copolymerized with a hydroxy-double terminated poly (arylene ether), hydroxyaryl-double ended polysiloxane and aromatic diacid chloride (Arylene ether) -polysiloxane multiblock copolymer, which is the resultant product.

The hydroxy-double-terminated poly (arylene ether) may have the following structure:

Where x and y are each independently 0 to about 100 when the sum of x and y is at least 2; Each of Q ¹ is independently selected from the group consisting of halogen, C ₁ -C ₁₂ hydrocarbylthio, C ₁ -C ₁₂ hydrocarbyloxy, C ₂ -C ₁₂ halohydrocarbyloxy, wherein at least two carbon atoms are halogen and oxygen atoms And an unsubstituted or substituted C ₁ -C ₁₂ hydrocarbyl (when the hydrocarbyl group is not a tertiary hydrocarbyl); Q ² each independently represent hydrogen, halogen, C ₁ -C ₁₂ hydrocarbyl thio, C ₁ -C ₁₂ hydrocarbyl oxy, C ₂ -C ₁₂ halo-hydrocarbyl-oxy (at least two carbon atoms are halogen and oxygen And the unsubstituted or substituted C ₁ -C ₁₂ hydrocarbyl (when the hydrocarbyl group is not a tertiary hydrocarbyl); L has the following structure,

Wherein each of R ¹ and R ² is independently selected from the group consisting of hydrogen, halogen, C ₁ -C ₁₂ hydrocarbylthio, C ₁ -C ₁₂ hydrocarbyloxy, C ₂ -C ₁₂ halohydrocarbyloxy (containing at least two carbons Wherein the atom is selected from the group consisting of a halogen and an oxygen atom, and an unsubstituted or substituted C ₁ -C ₁₂ hydrocarbyl wherein the hydrocarbyl group is not a tertiary hydrocarbyl; z is 0 or 1; Y has a structure selected from the group consisting of:

Wherein R ³ -R ⁶ are each independently hydrogen or C ₁ -C ₁₂ hydrocarbyl.

In some embodiments, the hydroxy-double-terminated poly (arylene ether) has the following structure:

Wherein each Q < ³ > is independently methyl or di-n-butylaminomethyl; each of a and b is independently from 0 to about 100 when the sum of a and b is on average from about 3 to about 100. In some embodiments, the sum of a and b averages from about 4 to about 30.

The aromatic diacid chlorides used in the polyesterification process include, for example, terephthaloyl chloride, isophthaloyl chloride, 4,4'-biphenyldicarbonyl chloride, 3,3'-biphenyldicarbonyl chloride, (Benzoyl chloride), 3,3'-oxybis (benzoyl chloride), 3,4'-oxybis (benzoyl chloride), 4,4'-biphenyl dicarbonyl chloride, (Benzoyl chloride), 3,3'-sulfonylbis (benzoyl chloride), 3,4'-sulfonylbis (benzoyl chloride), naphthalene-2,6-dicarbonyl chloride, Lt; / RTI > In some embodiments, the aromatic diacid chloride is comprised of terephthaloyl chloride.

As noted above, when the poly (arylene ether) -polysiloxane multi-block copolymer is prepared by a polyesteration process, it is composed of at least two poly (arylene ether) blocks and at least two polysiloxane blocks. However, it may contain a greater number of each type of block. For example, in some embodiments, the poly (arylene ether) -polysiloxane multi-block copolymer is comprised of from about 5 to about 25 poly (arylene ether) blocks and from about 10 to about 30 polysiloxane blocks.

One advantage of the composition of the present invention is that it exhibits substantial property improvements over the corresponding composition substituted with a poly (arylene ether) instead of a poly (arylene ether) -polysiloxane block copolymer of the composition of the present invention. It is surprising that such improvements can be achieved in relatively low total siloxane loading. For example, in some embodiments, the poly (arylene ether) -polysiloxane block copolymer provides about 1 to about 5 weight percent polysiloxane in the composition. Within the range of about 1 to about 5 weight percent, the polysiloxane contribution of the poly (arylene ether) -polysiloxane block copolymer can be from about 2 to about 4 weight percent, specifically from about 2 to about 3 weight percent.

Further details regarding the polyesterization process and the poly (arylene ether) -polysiloxane multi-block copolymers prepared thereby may be found in co-pending U. S. Patent Application No. 12 / 644,144, filed December 22, 2009 have.

In some embodiments, the compatibilized blend comprises, based on the total weight of the polyamide and poly (arylene ether) -polysiloxane block copolymer, from about 40 to about 90 parts by weight of a polyamide and from about 10 to about 60 parts by weight of a poly (Arylene ether) -polysiloxane block copolymer. Within the range of about 40 to about 90 parts by weight, the amount of polyamide may be at least about 45 parts by weight. Also within the range of from about 40 to about 90 parts by weight, the amount of polyamide may be up to about 80 parts by weight, specifically up to about 70 parts by weight, more specifically up to about 60 parts by weight. Within the range of about 10 to about 60 parts by weight, the amount of poly (arylene ether) -polysiloxane block copolymer can be at least about 20 parts by weight, specifically at least about 30 parts by weight, and more particularly at least about 40 parts by weight. Also within the range of about 10 to about 60 parts by weight, the amount of the poly (arylene ether) -polysiloxane block copolymer can be up to about 55 parts by weight.

The composition comprises from about 55 to about 95 weight percent of the compatibilized blend, based on the total weight of the composition. The amount of the compatibilized blend is selected such that the sum of all polyamides, all poly (arylene ether) -polysiloxane block copolymers, optional poly (arylene ether) s, and optional optional compatibilizers used to form the compatibilized blend . The amount of poly (arylene ether) is in the range of about 55 to about 95 weight percent, and the amount of poly (arylene ether) is about 65 to about 90 weight percent, specifically about 75 to about 87 weight percent, more specifically about 80 to about 87 weight percent, Lt; / RTI >

In some embodiments, a compatibilizer is used to facilitate the formation of a commercialized blend of polyamide and poly (arylene ether) -polysiloxane block copolymer. As used herein, the expression "compatibilizing agent" refers to a polyfunctional compound that interacts with a poly (arylene ether) -polysiloxane block copolymer, a polyamide resin, or both. These interactions may be chemical (e.g., grafting) and / or physical (e.g., affecting the surface characteristics of the dispersed phases). In either case, the resulting commercialized blend exhibits improved compatibility, as evidenced by improved impact strength, mold knit line strength and / or tensile elongation. As used herein, the expression "commercialized blend" refers to a composition that is physically and / or chemically compatible with a compatibilizing agent, and may also include, for example, a compatible-enhanced dibutyl (meth) acrylate Refers to a blend of polyamide and poly (arylene ether) -polysiloxane block copolymers that are physically compatible without such agents).

Examples of compatibilizers which may be used are liquid diene polymers, epoxy compounds, oxidized polyolefin waxes, quinones, organosilane compounds, polyfunctional compounds, functionalized poly (arylene ether) s, functionalized poly Ether) -polysiloxane block copolymers and combinations thereof. The compatibilizer is also described further in U.S. Patent No. 5,132,365 to Gallucci and U.S. Patent No. 6,593,411 to Koevoets et al., As well as U.S. Patent Application Publication No. US 2003/0166762 Al to Koevoets et al.

In some embodiments, the compatibilizer is comprised of a polyfunctional compound. There are usually three types of multifunctional compounds available as compatibilizers. A first type of multifunctional compound is a mixture of (a) and (b) both in the molecule, namely (a) a carbon-carbon double bond or a carbon- carbon triple bond, and (b) at least one carboxylic acid, anhydride, An amino, an epoxy, an orthoester or a hydroxy group. Examples of such multifunctional compounds are maleic acid; Maleic anhydride; Fumaric acid; Glycidyl acrylate, itaconic acid; Aconitic acid; Maleimide; Maleic hydrazide; Reaction products obtained from diamines and maleic anhydrides, maleic acid, fumaric acid and the like; Dichloromaleic anhydride; Maleic acid amide; Unsaturated dicarboxylic acids (e.g., acrylic acid, butenoic acid, methacrylic acid, ethyl acrylic acid, pentenoic acid, decenoic acid, undecenoic acid, dodecenoic acid ), Linoleic acid, etc.); Anhydrides, esters or acid amides of said unsaturated carboxylic acids; Unsaturated alcohols such as alkanol, crotyl alcohol, methylvinylcarbinol, 4-penten-1-ol, 1,4-hexadiene- 5-dimethyl-3-hexene-2,5-diol, and alcohols of formula C _n H _{2n -5} OH, C _n H _{2n -7} OH and C _n H _{2n -9} OH where n is a positive integer less than 30 )); The -OH group (s) of the unsaturated alcohol is replaced with -NH ₂ An unsaturated amine obtained by substitution with group (s); Functionalized diene polymers and copolymers; And combinations comprising at least one of the foregoing. In one embodiment, the compatibilizer is comprised of maleic anhydride and / or fumaric acid.

A second type of multifunctional compatibilizing agent is a mixture of (a) and (b), that is to say all of the following groups: (a) a group represented by formula (OR) wherein R is hydrogen or alkyl, aryl, acyl or carbonyl dioxy ) And (b) at least two groups, each of which may be the same or different, selected from carboxylic acids, acid halides, anhydrides, acid halide anhydrides, esters, orthoesters, amides, imides, . Typical compatibilizers belonging to this group are aliphatic polycarboxylic acids, acid esters, and acid amides of the formula:

Wherein R 'is a linear or branched, saturated aliphatic hydrocarbon having from 2 to 20, more specifically from 2 to 10, carbon atoms; R ^I is hydrogen or an alkyl, aryl, acyl or carbonyl dioxy group having 1 to 10, in particular 1 to 6, more particularly 1 to 4 carbon atoms; Each R ^II is independently hydrogen or an alkyl or aryl group having 1 to 20, more specifically 1 to 10 carbon atoms; R ^III And R ^IV Each is independently hydrogen or an alkyl or aryl group having 1 to 10, in particular 1 to 6, more particularly 1 to 4 carbon atoms; m is equal to 1, (n + s) is equal to or greater than 2, more specifically equal to 2 or 3, n and s are each equal to or greater than 0, (OR ^I ) is alpha or beta with respect to the carbonyl group, The two carbonyl groups are separated by 2 to 6 carbon atoms. Obviously, R ^I , R ^II , R ^III And R ^IV Can not be aryl when each substituent has less than 6 carbon atoms.

Suitable polycarboxylic acids include, for example, citric acid, malic acid, and agaricic acid (including various commercial forms thereof, such as anhydrous and hydrated acids); And combinations comprising at least one of the foregoing. In one embodiment, the compatibilizer is comprised of citric acid. Examples of esters useful herein include, for example, acetyl citrate, monostearyl and / or distearyl citrate and the like. Suitable amides useful herein include, for example, N, N'-diethyl citrate amide; N-phenyl citrate amide; N-dodecyl citrate amide; N, N'-didodecyl citrate amide; And N-dodecylmalonic acid. Derivatives include salts thereof, including salts with amines and alkali and alkali metal salts. Examples of suitable salts include calcium malate, calcium citrate, potassium malate and potassium citrate.

A third type of multifunctional compatibilizing agent is a mixture of (a) and (b) both in the molecule, namely (a) an acid halide group and (b) at least one carboxylic acid, anhydride, ester, epoxy, orthoester, Preferably a carboxylic acid or anhydride group. Examples of compatibilizers belonging to this group include trimellitic anhydride acid chloride, chloroformyl succinic anhydride, chloroformylsuccinic acid, chloroformyl glutaric anhydride, chloroformyl glutaric anhydride, Acid, chloroacetyl succinic anhydride, chloroacetyl succinic acid, trimellitic acid chloride, and chloroacetyl glutaric acid. In one embodiment, the compatibilizer is comprised of anhydrous trimellitic acid chloride.

The compatibilizer may be added directly to the melt blend or may be pre-reacted with one or both of the poly (arylene ether) -polysiloxane block copolymer and polyamide, as well as any other resin material employed in the preparation of the composition (pre-reacted). When at least a portion of the compatibilizer is pre-reacted with some or all of the poly (arylene ether) -polysiloxane block copolymer in a solution or melt of a suitable solvent, using the plurality of compatibilizers, especially the polyfunctional compound , A much greater improvement in compatibility is found. Such preliminary reaction is believed to allow the compatibilizer to react with and consequently functionalize the poly (arylene ether) -polysiloxane block copolymer. For example, a poly (arylene ether) -polysiloxane block copolymer may be pre-reacted with maleic anhydride to form anhydride-functionalized poly (arylene ether) -polysiloxane block copolymer to form a non-functionalized poly Arylene ether) -polysiloxane block copolymers with improved compatibility with polyamides.

When a compatibilizer is used in the preparation of the composition, the amount will vary depending on the particular compatibilizer selected and the particular polymer system to which it is added. In some embodiments, the amount of compatibilizing agent may be from about 0.1 to about 1% by weight, specifically from about 0.2 to about 0.8% by weight, more specifically from about 0.3 to about 0.6% by weight, based on the total weight of the composition .

The composition may optionally further comprise a poly (arylene ether). The term "poly (arylene ether)" as used herein is distinguished from "poly (arylene ether) -polysiloxane block copolymer ". "Poly (arylene ether)" refers to a polymer composed of a plurality of arylene ether units and siloxane units excluded. The poly (arylene ether) may be, for example, a homopolymer formed by the oxidative polymerization of a single monovalent phenol; (Including those described above in the context of the oxidation copolymerization process for the preparation of poly (arylene ether) -polysiloxane block copolymers) and other monohydric phenols or secondary phenols which may be dihydric phenols or polyhydric phenols A random copolymer formed by oxidation-copolymerization of the polymer; Or a block copolymer formed by sequential oxidative polymerization of at least two monohydric phenols. The poly (arylene ether) may be provided as part of the poly (arylene ether) -polysiloxane block copolymer reaction product described above. Alternatively or additionally, the poly (arylene ether) may be added separately.

Suitable poly (arylene ethers) include those characterized by a weight average molecular weight and a peak molecular weight, wherein the ratio of weight average molecular weight to peak molecular weight is from about 1.3: 1 to about 4: 1. Such poly (arylene ether) s and their preparation methods are described in co-pending US patent application Ser. No. 61 / 224,936 filed on July 13, 2009. Suitable poly (arylene ethers) also include poly (2,6-dimethyl-1,4-phenylene ether), wherein the poly (2,6-dimethyl- (2,6-dimethyl-1, 4-phenylene ether) prepared by dissolving the polymer in toluene, precipitating from methanol, reslurrying and separating, has a single molecular weight in the molecular weight range of 250 to 1,000,000 atomic mass units (2,6-dimethyl-1,4-phenylene ether) having a monomodal molecular weight distribution and no more than 2.2% by weight having a molecular weight greater than 15 times the number average molecular weight of the whole purified sample . When the purified sample is separated into six equal weight poly (2,6-dimethyl-l, 4-phenylene ether) weight fractions with reduced molecular weight, the sample comprises at least a monomer comprising at least a terminal morpholine- And the first, highest molecular weight fraction consisting of 10 mole% of poly (2,6-dimethyl-1,4-phenylene ether). These poly (arylene ether) s and their preparation methods are described in co-pending US patent application 12 / 495,980 filed July 1, 2008.

When present, the poly (arylene ether) is present in an amount of from about 1 to about 35 weight percent, specifically from about 5 to about 30 weight percent, and more specifically from about 10 to about 25 weight percent, based on the total weight of the composition May be included in the composition. The poly (arylene ether) is considered to be part of the commercialized blend.

The composition consists of a metal dialkyl phosphinate. In some embodiments, the metal dialkyl phosphinate has the formula:

Wherein R < ⁹ > And R ¹⁰ are independently C ₁ -C ₆ alkyl, phenyl, or aryl; M is calcium, magnesium, aluminum or zinc; d is 2 or 3; In some embodiments, R < ⁹ > And R ¹⁰ is ethyl, M is aluminum and d is 3; That is, the metal dialkyl phosphinate is aluminum tris (diethyl phosphinate).

The composition comprises the metal dialkyl phosphinate in an amount of about 1 to about 12 weight percent based on the total weight of the composition. Within this range, the metal dialkyl phosphinate may be from about 2 to about 10 weight percent, specifically from about 4 to about 8 weight percent.

In addition to the compatibilized blend and the metal dialkyl phosphinate, the composition may optionally further comprise glass fibers. Suitable glass fibers include those having a diameter of from about 7 to about 20 micrometers, specifically from about 10 to about 15 micrometers. Glass fibers may also include coatings (also known as sizing) to improve compatibility with polyamides. When present, the glass fibers may be used in an amount of about 2 to about 40 weight percent, based on the total weight of the composition. In some embodiments, the amount of glass fiber is from about 5 to about 15 weight percent. In another embodiment, the amount of the glass fibers is about 25 to about 40 wt%.

In a very specific embodiment, the composition has the following characteristics. It is comprised of from about 75 to about 90 weight percent of a blended blend of polyamide and poly (arylene ether) -polysiloxane block copolymer, and from about 2 to about 10 weight percent metal dialkyl phosphinate. It is further comprised of from about 5 to about 15 weight percent glass fibers. The compatibilized blend comprises 40 to 60 parts by weight of a polyamide and 40 to 60 parts by weight of a poly (arylene ether) -polysiloxane block copolymer, based on the total weight of the polyamide and poly (arylene ether) Is commercialized. The polyamide is composed of polyamide-6,6. The poly (arylene ether) -polysiloxane block copolymer comprises about 90 to about 99 parts by weight of a monohydric phenol and about 1 to about 10 parts by weight of a hydroxy (meth) acrylate, based on the total weight of monohydric phenol and hydroxyaryl-terminated polysiloxane, Aryl-terminated polysiloxane and an aryl-terminated polysiloxane. The metal dialkyl phosphinate is composed of aluminum tris (diethylphosphinate).

The composition may exhibit excellent flame retardancy. For example, in some embodiments, the composition may be 2 millimeters or 1.6 millimeters or 1 millimeter when measured according to Laboratory Bulletin 94 "Flammability Test of Plastic Materials, UL 94 ", Vertical Combustion Flame Test, Indicates a flammability rating of V-1 or V-0 in the thickness of the millimeter. This test is described in the following example.

The composition may exhibit excellent ductility. One objective measure of ductility is notched Izod impact strength. In some embodiments, the composition exhibits a notched Izod impact strength of at least 5 kilojoules (kJ) / m2, specifically 5 to about 8 kJ / m2 when measured at 23 DEG C in accordance with ISO 180 / A1. Another objective measure of ductility is the tensile elongation at break. In some embodiments, the composition exhibits a tensile elongation at break of at least 1.5%, specifically 1.5 to 5%, more particularly 1.5 to 4%, as measured at 23 占 폚 in accordance with ASTM D638-08.

One embodiment comprises a composition comprising about 22 to about 85 weight percent polyamide, about 6 to about 57 weight percent poly (arylene ether) -polysiloxane block copolymer, and about 1 to 12 weight percent metal dialkyl phosphinate (All percentages by weight being based on the total weight of the composition) consisting of forming the composition by melt blending. Within the range of about 22 to about 85 weight percent, the amount of polyamide is from about 29 to about 75 weight percent, specifically from about 35 to about 65 weight percent, more specifically from about 35 to about 55 weight percent, By weight to about 35% by weight to about 45% by weight. The amount of the poly (arylene ether) -polysiloxane block copolymer ranges from about 15 to about 52 weight percent, specifically from about 25 to about 47 weight percent, and more specifically, from about 35 to about 57 weight percent, To about 47% by weight. Within the range of about 1 to 12 weight percent, the amount of the metal dialkyl phosphinate may be about 2 to about 10 weight percent, specifically about 4 to about 8 weight percent. All of the compositional variables described above in the context of the composition apply equally to the above method of forming the composition.

The melt blending is usually carried out at a temperature of from about 270 to about 320 캜, specifically from about 280 to about 310 캜, and more specifically from about 290 to about 300 캜. Apparatuses for melt blending are known in the art and include, for example, single and twin-screw extruders, Brabender mixers and extruders.

In a very specific embodiment, the method has the following features. The polyamide is composed of polyamide-6,6, and the amount of the polyamide is about 35 to about 45% by weight. The poly (arylene ether) -polysiloxane block copolymer comprises about 90 to about 99 parts by weight of a monohydric phenol and about 1 to about 10 parts by weight of a hydroxy (meth) acrylate, based on the total weight of monohydric phenol and hydroxyaryl-terminated polysiloxane, Is a product of the process consisting in oxidizing a monomer mixture consisting of an aryl-terminated polysiloxane. The amount of the poly (arylene ether) -polysiloxane block copolymer is from about 35 to about 47 weight percent. The metal dialkyl phosphinate is composed of aluminum tris (diethylphosphinate). The metal dialkyl phosphinate is used in an amount of about 2 to about 10 weight percent. The composition is further comprised of blending about 5 to about 15 weight percent glass fibers with the polyamide, the poly (arylene ether) -polysiloxane block copolymer and the metal dialkyl phosphinate.

Other embodiments include compositions made by any of the methods described above.

Still other embodiments include articles comprising the composition. Useful articles that may be made from the composition include electrical and automotive connectors, electrical devices such as switches, and electrical enclosures such as junction boxes, lighting enclosures, and sockets. Injection molding is currently the preferred method of forming an article from the composition.

The present invention includes at least the following embodiments.

Example 1: from about 55 to about 95 weight percent, based on the total weight of the composition, of a blended blend of polyamide and poly (arylene ether) -polysiloxane block copolymer; And from about 1 to about 12 weight percent of a metal dialkyl phosphinate.

Example 2: The composition of Example 1, wherein the compatibilized blend comprises from about 40 to about 90 parts by weight of polyamide and from about 10 to about 90 parts by weight, based on the total weight of the polyamide and poly (arylene ether) A composition comprising about 60 parts by weight of a poly (arylene ether) -polysiloxane block copolymer.

Example 3: As a composition of Example 1 or 2, the poly (arylene ether) -polysiloxane block copolymer was prepared by a process consisting of oxidation copolymerization of a monomer mixture consisting of a monohydric phenol and a hydroxyaryl-terminated polysiloxane Lt; / RTI >

Example 4: The composition of Example 3, wherein the monomer mixture comprises about 90 to about 99 parts by weight monovalent phenol and about 1 to about 10 parts by weight, based on the total weight of monohydric phenol and hydroxyaryl-terminated polysiloxane, Hydroxyaryl-terminated polysiloxane.

Example 5: The composition of Example 3 or 4, wherein the hydroxyaryl-double end polysiloxane comprises a plurality of repeating units having the structure:

(Wherein each R ⁷ is independently hydrogen, C ₁ -C ₁₂ hydrocarbyl or halo-C ₁ -C ₁₂ hydrocarbyl bilim); And two terminal units having the structure below.

C ₁ -C ₁₂ hydrocarbyl, C ₁ -C ₁₂ hydrocarbyloxy, or halogen, each of R ⁸ is independently hydrogen, C ₁ -C ₁₂ hydrocarbyl or C ₁ -C ₁₂ hydrocarbyl, C ₁₂ halo halocarbyl)

Example 6: A composition as in any of Examples 3-5, wherein the monohydric phenol is comprised of 2,6-dimethylphenol, and the hydroxyaryl-terminated polysiloxane has the structure:

(Wherein n is an average of about 5 to about 100)

Example 7: A composition according to any of embodiments 1-6, wherein the compatibilized blend is further comprised of a poly (arylene ether).

Example 8: A composition according to any of embodiments 1 to 7, wherein the metal dialkyl phosphinate has the formula:

(Wherein R < ⁹ > And R ¹⁰ are independently C ₁ -C ₆ alkyl, phenyl, or aryl; M is calcium, magnesium, aluminum or zinc; d is 2 or 3.)

Example 9: As the composition of Example 8, R ⁹ And R ¹⁰ is ethyl, M is aluminum, and d is 3.

Example 10: A composition according to any of embodiments 1-9, further comprising from about 2 to about 40 weight percent glass fibers.

Example 11: A composition according to any of embodiments 1 to 10 further comprising from about 5 to about 15 weight percent glass fibers.

Example 12: A composition according to any of embodiments 1 to 10 further comprising from about 25% to about 40% by weight of glass fibers.

Example 13: As a composition any of Examples 1-12, the poly (arylene ether) -polysiloxane block copolymer provides about 1 to about 5 weight percent polysiloxane to the composition.

Example 14: As any of the compositions of Examples 1 to 11 and 13, from about 75 to about 90 weight percent of a blended blend of polyamide and poly (arylene ether) -polysiloxane block copolymer, and from about 2 to about 10% by weight of a metal dialkyl phosphinate; From about 5 to about 15 weight percent glass fibers; The compatibilized blend comprises 40 to 60 parts by weight of a polyamide and 40 to 60 parts by weight of a poly (arylene ether) -polysiloxane block copolymer, based on the total weight of the polyamide and poly (arylene ether) Commercialized; Said polyamide being composed of polyamide-6,6; The poly (arylene ether) -polysiloxane block copolymer comprises about 90 to about 99 parts by weight of a monohydric phenol and about 1 to about 10 parts by weight of a hydroxy (meth) acrylate, based on the total weight of monohydric phenol and hydroxyaryl-terminated polysiloxane, Comprising the step of oxidation-copolymerizing a monomer mixture comprising an aryl-terminated polysiloxane; Wherein the metal dialkyl phosphinate is comprised of aluminum tris (diethyl phosphinate).

Example 15: about 22 to about 85 weight percent polyamide, about 6 to about 57 weight percent poly (arylene ether) -polysiloxane block copolymer, and about 1 to 12 weight percent metal dialkyl phosphinate (All percentages by weight being based on the total weight of the composition) of the composition by melt blending.

Example 16: As the method of Example 15, the polyamide is composed of polyamide-6,6; The amount of polyamide is from about 35 to about 45 weight percent; The poly (arylene ether) -polysiloxane block copolymer comprises about 90 to about 99 parts by weight of a monohydric phenol and about 1 to about 10 parts by weight of a hydroxy (meth) acrylate, based on the total weight of monohydric phenol and hydroxyaryl-terminated polysiloxane, Product of a process comprising oxidation-copolymerizing a monomer mixture comprising an aryl-terminated polysiloxane; The amount of said poly (arylene ether) -polysiloxane block copolymer is from about 35 to about 47 weight percent; The metal dialkyl phosphinate is composed of aluminum tris (diethylphosphinate); The amount of said metal dialkyl phosphinate is from about 2 to about 10 weight percent; Further comprising blending about 5 to about 15 weight percent glass fibers with the polyamide, the poly (arylene ether) -polysiloxane block copolymer and the metal dialkyl phosphinate.

Example 17: A composition prepared by any of the methods of Examples 15 or 16.

Example 18: An article consisting of any of the compositions of Examples 1-14 and 17.

The invention is further illustrated by the following non-limiting examples.

Preparation Example  One

This example illustrates the preparation of poly (arylene ether) -polysiloxane block copolymers by oxidative polymerization of 95 weight percent monovalent phenol in the presence of 5 weight percent hydroxyaryl-dual end polysiloxane.

The process is summarized in Table 1, where the "toluene source" is a mixture of toluene and toluene, which is either fresh (in Table 1 "fresh") toluene solvent or recycled from poly (arylene ether) Playback ");"DMBA level (%)" is the concentration of dimethyl-n-butylamine expressed as weight% relative to the weight of toluene; "Solids (%)" are the total weight of 2,6-dimethylphenol and eugenol-capped polysiloxane expressed as weight percentages based on the sum of the weights of 2,6-dimethylphenol, eugenol-capped polysiloxane and toluene ; "Polysiloxane chain length" is the average number of dimethylsiloxane (-Si (CH ₃ ) ₂ O-) units in the eugenol-capped polysiloxane; "Polysiloxane loading (%)" is the weight percent of eugenol-capped polysiloxane in the reaction mixture, based on the total weight of 2,6-dimethylphenol and eugenol-capped polysiloxane; The initial " 2,6-dimethylphenol (%) "represents the weight% of 2,6-dimethylphenol present in the reaction vessel at the initial stage of polymerization (oxygen introduction into the reaction vessel) relative to the total weight of 2,6- ; "O: 2,6-dimethylphenol molar ratio" is the molar ratio of atomic oxygen (provided as oxygen molecule) to 2,6-dimethylphenol maintained during the addition of 2,6-dimethylphenol; "Initial charge temperature (占 폚)" is the temperature (in degrees Celsius) of the reaction mixture when the initial charge of the monomer is added to the reaction vessel and when oxygen is initially introduced into the reaction mixture; "Addition temperature (C)" is the reaction temperature during the addition of 2,6-dimethylphenol; "Build temperature (C)" is the temperature expressed in degrees Celsius during the build phase of the reaction; "Ramp time (min)" is the time (expressed in minutes) during which the temperature is ramped from the addition temperature to the build temperature; Is the rate of change of temperature, expressed in degrees Celsius per minute, while the temperature is ramped from the addition temperature to the build temperature; "Reaction time (min)" is the total reaction time, expressed in minutes, that elapsed between the oxygen introduction moment and the oxygen cut-off instant. For all variables, the controlled monomer addition time is from 40 to 80 minutes from the start of the reaction (i.e., the initiation of the oxygen flow). The build time is measured from the end of the controlled monomer addition to the end of the reaction (i.e., the end of the oxygen flow); The build time was about 80 to 160 minutes.

The following general synthetic procedure was used. The reactor and the 2,6-dimethylphenol addition tank were rinsed with warm toluene and discarded. The reaction was purged with nitrogen to obtain an oxygen concentration of less than 1%. The reactor was charged with initial toluene (fresh or regenerated), and the toluene was stirred at 500 revolutions per minute (rpm). The temperature of the initial toluene was adjusted to the "initial charge" temperature specified in Table 1 and the temperature was maintained while the initial charge of 2,6-dimethylphenol was added from the addition tank to the reaction vessel. After the addition of the initial charge of 2,6-dimethylphenol was completed, the reaction vessel was charged with eugenol-capped polydimethylsiloxane, di-n-butylamine, dimethyl-n-butylamine, diamine and copper catalysts. The oxygen flow and the addition of additional monomer were initiated and the oxygen flow was adjusted to maintain a headspace concentration of less than 17%. During addition of the monomer addition, cooling of the water feed temperature was adjusted to maintain the specified temperature as "addition temperature (C)" in Table 1. After monomer addition was complete, the monomer addition line was flushed with toluene and the reaction temperature was increased to the specified temperature as "build temperature (C)" This temperature regulation was carried out at a rate specified in Table 1 as "ramp slope (° C / min)" for a time specified in Table 1 as "ramp time (min) ". The reaction was continued until a predetermined time point was reached. The predetermined endpoint is the time at which the target intrinsic viscosity and maximum siloxane bond is achieved, usually 80 to 160 minutes after the addition of 2,6-dimethylphenol is complete. When the time point was reached, the oxygen flow was stopped. The reaction mixture was then heated to 60 DEG C and pumped into a chelation tank containing an aqueous chelant solution. The reaction mixture was stirred and held at 60 < 0 > C for 1 hour. The light (organic) phase and the heavy (aqueous) phase were separated by decanting and the heavy phase discarded. A small amount of the light phase was sampled and precipitated with isopropanol for analysis and the remainder of the light phase was pumped into the precipitation tank to remove the methanol half-solvent (which may be replaced by isopropanol half-solvent) and 3 parts by weight of half- And combined with a light phase ratio. The precipitate was filtered to form a wet cake, which was re-slurried three times with the same semi-solvent and dried under nitrogen until a toluene concentration of less than 1 wt% was obtained.

The properties of the resulting products are summarized in Table 1. "Total volatile matter (%) ", which is the weight percent of volatile matter in the separated product, was determined by measuring% weight loss with drying at 110 ° C for 1 hour under vacuum; "Residual Cu (ppm)", expressed as parts per million by weight of copper element, was determined by atomic absorption spectrometry; With respect to the properties as a function of reaction time, remove the sample from the reactor, by adding a reaction mixture of 1 volume to the third volume of room temperature isopropanol produced a precipitate to settle (the dictionary without chelation of a metal catalyst), and this ¹ H NMR (to determine the siloxane weight% and siloxane bond efficiency) and intrinsic viscosity analysis prior to filtration, washing with isopropanol, and drying.

The number average molecular weight and the weight average molecular weight were determined as follows by gel permeation chromatography. The gel permeation chromatographs are calibrated using 8 polystyrene standards each with a narrow molecular weight distribution and collectively covering a molecular weight range of 3,000 to 1,000,000 grams / mole. The columns used were 1e3 and 1e5 Angstrom PLgel columns with 5 microliters 100 Angstrom PLgel guard columns. Chromatography was performed at 25 < 0 > C. The elution liquid was chloroform containing 100 parts by weight of di-n-butylamine. The elution flow was 1.2 milliliters per minute. The detector wavelength was 254 nanometers. A third-order polynomial function was fitted through the calibration points. The test sample is prepared by dissolving 0.27 grams of the separated block copolymer solids in 45 milliliters of toluene. Chromatograph the 50 microliter sample of the resulting solution. The number average molecular weight (M _n ) and weight average molecular weight (M _w ) values are calculated from the signals measured using a polystyrene calibration line. Then the value of formula M (PPE) = 0.3122 XM ( PS) 1.073 ( where M (PPE) is a poly (2,6-dimethyl-1,4-phenylene ether) molecular weight and M (PS) is a polystyrene of molecular weight being ) Is used to convert the molecular weight of polystyrene to the molecular weight of poly (2,6-dimethyl-1,4-phenylene ether).

In Table 1, "molecular weight < 10K (%)" is the weight percentage of the separated reaction product having a molecular weight of less than 10,000 atomic mass units, as determined by gel permeation chromatography; "Molecular weight> 100 K (%)" is the weight percent of the separated reaction product having a molecular weight greater than 10,000 atomic mass units as determined by gel permeation chromatography; "IV, end of reaction (dL / g)" is the intrinsic viscosity of the dry powder separated by precipitation from isopropanol, measured by Ubbelohde viscometer at 25 ° C in chloroform and expressed in terms of grams per gram; "IV, end of chelation (dL / g)" is the intrinsic viscosity of the product present in the post-chelation organic phase, separated by precipitation from isopropanol and measured by a Ubbelohde viscometer at 25 ° C in chloroform Gt; per gram &lt; / RTI &gt;;"M _w , termination of reaction (AMU)" is the weight average molecular weight of the product present in the reaction mixture at the end of the polymerization, dried and separated by precipitation from isopropanol, measured by gel permeation chromatography and expressed in atomic mass units; "M _n , termination of reaction (AMU)" is the number average molecular weight of the product present in the reaction mixture at the end of the polymerization, dried and separated by precipitation from isopropanol, measured by gel permeation chromatography and expressed in atomic mass units; "M _w / M _n , reaction terminated" is the ratio of the weight average molecular weight to the number average molecular weight of the product present in the reaction mixture at the end of the polymerization, which is separated by precipitation from isopropanol and dried; The term " M _w , chelating end (AMU) "is the weight average molecular weight of the product present in the organic phase after chelation, separated by precipitation from isopropanol, and measured by gel permeation chromatography and expressed in atomic mass units; The term " M _n , chelating end (AMU) "is the number average molecular weight of the product present in the organic phase after precipitation from the isopropanol and dried and after chelation, measured by gel permeation chromatography and expressed in atomic mass units; The term "M _w / M _n , chelation termination" is the ratio of the weight average molecular weight to the number average molecular weight of the product present in the organic phase after chelation, which is separated by precipitation from isopropanol and dried.

In Table 1, "siloxane weight% (%)" refers to the total weight of the dimethylsiloxane units in the separated product, based on the total weight of 2,6-dimethyl-1,4-phenylene ether units and dimethylsiloxane units in the isolated product As determined by ¹ H NMR using the protons labeled a and b in the configuration labeled "Formula (I) " below, calculated as:

here,

In the formula for X, "siloxane fluid Mn" is the number average molecular weight of the dimethylsiloxane units in the hydroxyaryl-terminated polysiloxane and "2,6 xylenol molecular weight" in the formula for Y is the molecular weight of 2,6-dimethylphenol . This is referred to as "siloxane wt%" in the metrology, which is an oversimplification in that it overlooks isolated product components that are not 2,6-dimethyl-1,4-phenylene ether units and dimethylsiloxane units. Nevertheless, this is a useful measure.

In Table 1, "siloxane incorporation efficiency (%)" is defined as the weight percent of dimethylsiloxane units in the separated product compared to the weight percent of dimethylsiloxane units in the total monomer composition used in the reaction mixture (from isopropanol Is determined by ¹ H NMR using the protons labeled a and b in the configuration labeled "Formula (I) &quot;, followed by the following: Calculated as:

The formula for weight percent siloxane in the product is given above,

Is the weight of hydroxyaryl-terminated polysiloxane used in the reaction mixture and "weight of 2,6 monomer loaded" is the weight of the 2,6-dimethylphenol used in the reaction mixture Weight. This is referred to as "siloxane bonding efficiency" in the metrology is an oversimplification in that it overlooks the possibility that small amounts of monomers and oligomers may be lost during the separation process. For example, it is theoretically possible for siloxane coupling efficiencies to exceed 100% if all hydroxy aryl-terminated polysiloxanes are coupled into the block copolymer and some arylene ether oligomers are lost in the separation process. Nevertheless, siloxane bond efficiency is a useful measure.

In Table 1, "tail (%)" is the% of 2,6-dimethylphenol in the end group configuration compared to the total 2,6-dimethylphenol residue, As determined by ¹ H NMR using a " tail "proton labeled with " a " and a proton labeled with a in the configuration labeled" Formula (I) " below,

The equation for Y is as above,

to be.

In Table 2, "biphenyl (%)" is the weight percent of 3,3 ', 5,5'-tetramethyl-4,4'-biphenol residue,

Is determined by ¹ H NMR using a "biphenyl" proton labeled with d in the configuration labeled "Formula (II)" below and a proton labeled with a in the configuration labeled "Formula (I) It is calculated as follows:

The equation for Y is as above,

Here, "biphenyl molecular weight" is the molecular weight of the 3,3 ', 5,5'-tetramethyl-4,4'-biphenol residue shown above.

"OH (ppm)" refers to the weight per million parts by weight of all hydroxy groups based on the total weight of the isolated sample, as determined by KP Chan et al. " ³¹ P NMR spectroscopy, Hydroxy group of the hydroxy group was analyzed by ³¹ P NMR after phosphorus derivatization of the hydroxyl group of the separated sample as described in " Easy Quantitative Analysis of the Hydroxy End Group of the Compound (I) (Macromolecules, volume 27, pages 6371-6375 .

Formula (I):

Formula (II):

Formula (III):

To characterize the Preparation Example 1 composition as a function of the molecular weight fraction, fractions from six gel permeation chromatography injections (total of 36 mg material injected) were collected using a Gilson fraction collector. The eluate eluted between the 12 and 25 run times was split into 60 tubes and then recombined to make 6 fractions each containing about 16.67% total material (determined from area% of chromatogram). A small fraction (200 [mu] l) of 5 fractions was analyzed by gel permeation chromatography to confirm successful fractionation. The remainder was used for ¹ H NMR analysis. The fraction used for NMR analysis was evaporated to dryness at 50 &lt; 0 &gt; C under a stream of nitrogen. Samples were analyzed by ¹ H NMR by adding 1 milliliter of deuterated chloroform (with tetramethylsilane as internal standard). The results given in Table 4 first show that all the fractions contain a substantial dimethylsiloxane content. The fact that no "tail%" was detected in the highest molecular weight fraction indicates that this fraction is essentially free of poly (arylene ether) homopolymer, i.e. an essentially pure block copolymer. Likewise, the fact that the largest "tail%" is observed in the lowest molecular weight fraction means that the poly (arylene ether) is biased towards the lower molecular weight fraction.

Preparation Example  2

This example illustrates the preparation of a poly (arylene ether) -polysiloxane block copolymer by oxidative polymerization of 80 wt% monohydric phenol in the presence of 20 wt% hydroxyaryl-double ended polysiloxane. The general procedure of Preparation Example 1 was followed except that the monomer mixture contained 80% by weight of monovalent phenol in the presence of 20% by weight of hydroxyaryl-double end polysiloxane. Reaction conditions and product properties are summarized in Table 3.

Preparation Example  3-4

This example illustrates the preparation of poly (arylene ether) -polysiloxane multiblock copolymers by reacting hydroxy-double terminated poly (arylene ether), hydroxyaryl-double ended polysiloxane and aromatic diacid chloride followed by capping the terminal hydroxy groups with benzoyl chloride &Lt; / RTI &gt; This is the presently preferred method of synthesizing poly (arylene ether) -polysiloxane block copolymers with high polysiloxane content. These examples include an acid chloride to hydroxyl mole ratio of 0.99: 1, a reaction temperature of 25 占 폚, a 3: 1 mole ratio of benzoyl chloride capping agent to the remaining hydroxyl groups on the multiblock copolymer, a 20 minute benzoyl chloride addition time, The benzoyl chloride reaction time followed by complete addition of chloride was used.

Detailed polymerization and separation procedures are as follows. Make a 20% w / v solution of the purified acid chloride in dichloromethane and transfer it to the addition funnel. Under anhydrous conditions, a 20 wt / vol% solution of hydroxy-double ended poly (arylene ether) in dichloromethane is prepared and transferred to a 2-neck reaction flask maintained at room temperature. While efficiently stirring in the reaction flask, a 20 wt / vol% solution of hydroxyaryl-double ended polysiloxane in dichloromethane is slowly poured into the reaction flask. When a homogeneous solution is obtained, a 20 wt / vol% solution of triethylamine in dichloromethane is added to the homogeneous reaction mass with continued stirring of the reaction flask contents. The terephthaloyl chloride solution is added dropwise and the rate of addition is maintained so that the entire solution is added within 60 minutes into the reaction flask. After the addition of the terephthaloyl chloride solution is completed, the reaction is continued for a further 3 hours. After a total reaction time of 4 hours, stirring of the reaction mixture is stopped and the reaction mixture volume is slowly poured into 6 volumes of methanol with vigorous stirring to allow the block copolymer product to settle. Continue stirring for at least one hour to facilitate the removal of trapped dichloromethane and the dissolution of the triethylammonium chloride salt in methanol. The methanol is decanted slowly, the product copolymer is separated (for example by filtration) and the product copolymer is dried at 80 ° C under vacuum.

The amounts of reagents and the properties of the resulting multiblock copolymers are summarized in Table 4. For the reagents in Table 4, "PPE-2OH, 0.09" represents an intrinsic viscosity of 0.09 deciliter per gram at 25 캜 chloroform, available as MX90-100-0 from SABIC Innovative Plastics, and an average of about 1.9 terminal hydroxyl groups per molecule Bis (4-hydroxy-3,5-dimethylphenyl) propane (CAS Registry No. 1012321-47-9) and 2,6-xylenol; "Eugenol-D10" is a eugenol-double-ended polydimethylsiloxane (CAS registry number 156065-00-8) having an average of about 10 polydimethylsiloxane units per molecule, available as Y-17126 from Momentive Performance Materials. "PPE-2OH, 0.09 (wt%)" is the weight percent of "PPE-2OH, 0.09" reagent based on the total weight of "PPE-2OH, 0.09" reagent and "Eugenol-D10" reagent. "Eugenol-D10 (wt.%)" Is the wt.% Of "eugenol-D10" reagent based on the total weight of "PPE-2OH, 0.09" reagent and "eugenol-D10" reagent.

For the properties of Table 4, "PPE bond (wt%)" refers to the weight percent of the poly (arylene ether) block in the product multiblock copolymer, based on the total weight of the poly (arylene ether) Determined by nuclear magnetic resonance spectroscopy ( ¹ H NMR); "Siloxane bond (wt%)" is the weight percent of polysiloxane block in the product multi-block copolymer, based on the total weight of the poly (arylene ether) block and polysiloxane block, as determined by ¹ H NMR; "M _n (amu)" is the number average molecular weight of the product multi-block copolymer determined by gel permeation chromatography using a polystyrene standard; "M _w (amu)" is the weight average molecular weight of the product multi-block copolymer determined by gel permeation chromatography using polystyrene standards; "M _w / M _n " is the ratio of weight average molecular weight to polydispersity index or number average molecular weight; "Residual -OH terminal (ppm)" is the free (distal), with a content of hydroxyl groups, which is ^"31 P NMR of poly (2,6-dimethyl-1,4-phenylene oxide) by the spectrometer, such as a hydroxyl Chan KP As determined by &lt; ³¹ &gt; P NMR after phosphorus derivatization of the hydroxyl groups of the separated sample as described in "Easy Quantitative Analysis of End Groups" (Macromolecules, volume 27, pages 6371-6375 (1994)); "DSC T _g (C)" is the glass transition temperature of the poly (arylene ether) block, as determined by differential scanning calorimetry; "TGA decomposition peak (C)" is the peak temperature in the weight-to-temperature derivative graph, as determined by an inductive thermogravimetric analysis (dTGA); The "MVR at &lt; RTI ID = 0.0 &gt; 280 C / 2.16 Kg" is &lt; / RTI &gt; a melt volume- flow rate, expressed in milliliters per minute (mL / 10 min), measured in accordance with ASTM D1238-04c using a temperature of 280 C and a load of 2.16 Kg. ; "Tensile modulus (MPa)" is the tensile modulus, expressed in megapascals (MPa), measured at 23 ° C in accordance with ASTM D638-08; "Breaking tensile stress (MPa)" is the tensile stress at break, expressed in megapascals, measured at 23 ° C in accordance with ASTM D638-08; "Break elongation (%)" is the tensile elongation at break, expressed as a percent, measured at 23 ° C in accordance with ASTM D638-08; "Hardness (Shore D)" is Shore D durometer hardness, expressed in units, measured at 23 ° C in accordance with ASTM D2240-05; At 23 DEG C and 0 DEG C, expressed in kilojoules per square meter, measured in accordance with ISO 180 / A1, "NII, 23 DEG C (kJ / A notched Izod impact strength value; &Quot; MAI total energy, 23 占 폚 (J) &quot;, and "MAI total energy, 0 占 폚 (J)>, measured at 23 占 폚 and 0 占 폚, respectively, in a disc of 3.2 mm thickness, 102 mm diameter according to ASTM D3763-08, (D) "after the reported value indicates ductile failure, and" (B) "after the reported value is the brittle fracture (brittle) failure; "Tension set, 48 hours (%)" was measured according to ASTM D412-06ae2; "Trouser tear strength, T type (kN / m)" was measured according to ASTM D624-00 (2007); "Insulation strength (kV / mm)" was measured according to ASTM D149-09 at a frequency of 500 volts / sec; The dielectric constant ("Dk") and loss factor ("Df") were determined according to ASTM D150-98 (2004); The volume resistivity expressed in ohm-cm and the surface resistivity expressed in ohm were measured at 23 DEG C according to ASTM D275-07.

In addition, in Table 4, "UL 94 Grade, 2 mm" and "UL 94 Grade, 1.6 mm" are respectively 2 mm and 2 mm according to the undergraduate laboratory bulletin 94 "Flammability test of plastic material, UL 94" It is the vertical combustion test grade measured at a sample thickness of 1.6 millimeters. In this process, a test bar having a dimension of 125 x 12.59 millimeters and a specific thickness is mounted vertically. Apply a 3/4 inch flame to the end of the test strip for 10 seconds and remove. UL 94 FOT T1, 2 mm (sec) "and" UL 94 FOT T1, 1.6 mm (sec) " in Table 4 are used to calculate the standard deviation "). Reapply the flame again for 10 seconds and remove. (UL 94 FOT T2, 2 mm (sec) and "UL 94 FOT T2, 1.6 mm (sec)" in Table 4). For class V-0, the individual burning time from primary or secondary flame application can not exceed 10 seconds; The total burning time for any five samples can not exceed 50 seconds; Drip particles igniting cotton gauze pieces placed below the specimen are not allowed; Burn-to-clamps are also not allowed. For class V-1, the individual burning time from primary or secondary flame applications can not exceed 30 seconds; The total burn time for any five samples can not exceed 250 seconds; Drip particles igniting cotton gauze pieces placed underneath the specimen are not allowed. For class V-2, the individual burning time from primary or secondary flame application can not exceed 30 seconds; The total burn time for any five samples can not exceed 250 seconds; Drip particles igniting cotton gauze pieces placed underneath the specimen are allowed, but burn-to-clamps are not allowed. "ND 94 drip, 2 mm" and "UL 94 drip, 1.6 mm" are visual observations of the dripping measured during the vertical combustion test at sample thicknesses of 2 mm and 1.6 mm, The value is that there is no observed drip, and the "D" value corresponds to when at least one drip is observed. The smoke density parameters "DS4 (minutes)" and "DSMax (minutes)" were measured in accordance with ASTM E662-09.

Examples 1-3, Comparative Example  1-5

These experiments illustrate the effect of the amount of poly (arylene ether) type and metal dialkyl phosphinate.

Table 5 summarizes the components used in the above Examples.

Eight poly (arylene ether) -polyamide compositions were prepared using the components and amounts listed in Table 6, wherein the amounts of all components are parts by weight. In these compositions, the amount of metal dialkyl phosphinate varies from 0 to 6% by weight and the poly (arylene ether) type is a poly (arylene ether) homopolymer or a poly (arylene ether) homopolymer having a polysiloxane content of 5% Rheneether) -polysiloxane block copolymer. The blend formulations were prepared by dry blending poly (arylene ether) or poly (arylene ether) -polysiloxane block copolymer, citric acid, stabilizer and flame retardant. This mixture was fed into the extruder at the upstream or neck position. The polyamide-6,6 was supplied using a separate feeder but was also added to the neck position. The glass fibers were fed using another separate feeder, but these fibers were added at downstream locations. The extruder used was a 30-millimeter Werner-Pfleiderer twin-screw extruder. The extruder was set at a barrel temperature of 290-300 DEG C and a die temperature of 300 DEG C, a screw rotation of 300 revolutions per minute (rpm), and a throughput rate of about 20 kilograms per hour. The amount of ingredients is expressed in parts by weight. The compositions were injection molded in an 85 ton Van Dorn injection molding machine. Prior to molding, the pellets were dried at 110 ° C (230 ° F) for 4 hours. The injection molding conditions were as follows. The injection molding was set at a temperature of 90 ° C (194 ° F) and the heating zones of the injection molding machine were all set at 300 ° C (572 ° F).

The properties of the compositions are summarized in Table 6. The flexural modulus and flexural strength, expressed in megapascals (MPa), respectively, were measured at 23 DEG C according to ASTM D790-07e1. The heat deflection temperature expressed in degrees Celsius was measured under a load of 1.8 and 0.45 megapascals according to ASTM D648-07. The notched and unnotched Izod impact strengths expressed in kiloJoules per square meter were measured at 23 DEG C in accordance with ISO 180. The tensile modulus expressed in megapascals, the yield tensile strength expressed in megapascals, and the percent elongation at break, expressed in%, were measured at 23 DEG C in accordance with ASTM D638-08. The melt volume flow rates expressed in milliliters per 10 minutes were measured at 280 占 폚 and 5 kg according to ASTM D1238-04c. The melt viscosity, expressed in Pascal-sec (Pa-s), was measured according to ASTM D3835-08 at 280 &lt; 0 &gt; C and 1,000 s ^-1 , 1,500 s ^-1 , 3,000 s ^-1 , and 5,000 s ^-1 . The blend with the poly (arylene ether) -polysiloxane block copolymer, as compared to the blend with the poly (arylene ether), has a higher notched Izod impact strength (4 out of 4 comparisons) and a higher breaking tensile elongation (3 out of 4 comparisons). &Lt; / RTI &gt; The blend with the poly (arylene ether) -polysiloxane block copolymer exhibited a lower melt viscosity (15 out of 16 comparisons) as compared to the blend with poly (arylene ether).

The flammability test was carried out according to Underwriter's laboratory bulletin 94 "Flammability test of plastic material, UL 94", vertical combustion flame test. The flame bar had a length of 125 millimeters, a width of 12.5 millimeters and a thickness of 2.0 millimeters. The flame bar is mounted vertically and a 1.9 centimeter (3/4 inch) flame is applied to the end of the test bar for 10 seconds and removed. In this test, the time during which the sample self-extinguishes (primary combustion time) is measured for 50 samples, and the standard deviation is calculated. The number of samples burned longer than 10 seconds is given in Table 6. Reapply the flame again for 10 seconds and remove. Measure the time that the sample self-extinguishes (secondary combustion time) and calculate the standard deviation. For the most preferred grade V-0, the individual combustion time from the primary or secondary flame application can not exceed 10 seconds; The total burning time for any five samples can not exceed 50 seconds; Drip particles igniting cotton gauze pieces placed below the specimen are not allowed; Burn-to-clamps are also not allowed. For class V-1, the individual burning time from primary or secondary flame applications can not exceed 30 seconds; The total burn time for any five samples can not exceed 250 seconds; Drip particles igniting cotton gauze pieces placed underneath the specimen are not allowed. For class V-2, the individual burning time from primary or secondary flame application can not exceed 30 seconds; The total burn time for any five samples can not exceed 250 seconds; Drip particles igniting cotton gauze pieces placed underneath the specimen are allowed, but burn-to-clamps are not allowed. A composition that does not meet the V-2 criteria is considered to have failed. The UL 94 vertical combustion rating for each composition is given in Table 6. The results show that, for a given level of metal dialkyl phosphinates, samples with poly (arylene ether) -polysiloxane block copolymer exhibit improved flame retardancy than samples with poly (arylene ether). Among the samples with the poly (arylene ether) -polysiloxane block copolymer, the sample without the metal dialkylphosphinate (Comparative Example 2) failed the vertical burning test, but only 2 parts by weight of the metal dialkylphosphinate Addition was sufficient to obtain the highest grade of V-0 (Example 1).

Briefly, blends with poly (arylene ether) -polysiloxane block copolymers and metal dialkyl phosphinates compared to blends with poly (arylene ether) exhibit improved flame retardance and improved mechanical properties. This would not have been possible by adjusting only the metal dialkylphosphinate concentration, since an increase in flame retardant concentration usually accompanies degradation of mechanical properties.

Substitution of poly (arylene ether) with poly (arylene ether) -polysiloxane block copolymer also affects the shape of the resulting blend. Electron microscopic photographs corresponding to Comparative Example 1, Comparative Example 2, Comparative Example 5 and Example 3 are shown in Figs. 1-4. Prior to electron microscopic analysis, the exposed surface of the sample was "etched" in toluene for 15 seconds to dissolve the dispersed poly (arylene ether) phase and then sputter-coated with a thin gold layer, Respectively. Thus, the dispersed poly (arylene ether) phase appears void in electron micrographs. In the case of Comparative Examples 1 and 2 in which there is no metal dialkyl phosphinate, the blend of Comparative Example 1 with 1 / poly (arylene ether) is shown in Comparative Example 2 with 2 / poly (arylene ether) -polysiloxane block copolymer (0.33 micrometer &lt; 2 ^&gt; ) smaller than the blend (0.55 micrometer ² ). Surprisingly, this tendency is reversed for Comparative Examples 5 and 3 which contain metal dialkyl phosphinates. For such samples, the Comparative Example 5 blend with Figure 3 / poly (arylene ether) showed a larger average projection than the Example 3 blend (Figure 1) with the poly (arylene ether) -polysiloxane block copolymer (1.07 micrometer ² ) &Lt; / RTI &gt; area (1.65 micrometer ² ).

Preparation Example  5 and 6, Comparative Example  6 and 7

These comparative examples include the incorporation of polysiloxane content into poly (arylene ether) -polyamide compositions via pre-compounding of poly (arylene ether), amino-functionalized polysiloxane and citric acid For example. While not wishing to be bound by any particular theory of operation, the inventors of the present invention have found that pre-mixing of poly (arylene ether), amino-functionalized polysiloxane and citric acid forms polysiloxane grafts on the poly (arylene ether) (I.e., forming a poly (arylene ether) - graft-polysiloxane copolymer).

The compositions are summarized in Table 7. Preparation Examples 5 and 6 were analyzed by ¹ H NMR to determine the weight percent of silicon fluid actually bonded or reacted into the functionalized poly (arylene ether). To this end, the as-compounded sample was analyzed by ¹ H NMR in deuterated chloroform to obtain the "incorporated siloxane (wt%)" value of Table 7. Separately, samples as mixed were dissolved in chloroform and precipitated with a mixture of 21% by volume acetone and 79% by volume methanol and then dissolved in deuterated chloroform for &lt; ¹ &gt; H NMR analysis to give the "bound siloxane (% By weight) " Comparing the nominal siloxane content of 7% by weight with the value of the "combined siloxane (wt.%)" Value in Table 7 indicates that a significant fraction of the siloxane fluid was lost during mixing (possible through the extruder vacuum outlet) . Comparing the "incorporated siloxane (wt%)" value to the "bound siloxane (wt%)" indicates that less than half of the combined siloxane is chemically bound to the poly (arylene ether).

Table 7 summarizes the mechanical properties of Comparative Examples 6 and 7 which combine Preparation Examples 4 and 5, respectively. The properties of Comparative Examples 6 and 7 can be compared to those of Example 3 of Table 6. [ Example 3 shows improved notched Izod impact strength and improved breaking elongation at break compared to Comparative Examples 6 and 7. This indicates that it is preferable that silicon be incorporated into the backbone of the poly (arylene ether) rather than as a graft.

Table 7 also summarizes the flame retardant properties of Comparative Examples 6 and 7. This characteristic is significantly inferior to that of Example 3 which achieves a V-0 rating and does not burn longer than 10 seconds out of 50 pyrotechnic bars.

Micrographs showing the shapes of Comparative Examples 6 and 7 are shown in Figures 5 and 6, respectively. FIG image of a 5 / Comparative Example 6 represents a particle having an average projected area of 2.45 microns ^2, the image of Fig. 6 / Comparative Example 7 represents a particle having an average projected area of 5.36 microns ^2. The higher citric acid concentration of Comparative Example 6 compared to Comparative Example 7 was associated with a smaller particle size (i.e., better commercialization of polyamide and poly (arylene ether)). The particle size values of Comparative Examples 6 and 7 are substantially larger than that of FIG. 4 / Example 3 (1.07 micrometer ² ).

Example 4-9

These examples illustrate compositions comprising a polyamide, a poly (arylene ether) -polysiloxane block copolymer and a metal dialkyl phosphinate. These compositions comprise about 30% by weight of glass fibers. The composition and properties are summarized in Table 8.

These performance examples collectively indicate that the glass-filled blend of poly (arylene ether) and polyamide is flexible and flame retardant when the poly (arylene ether) is comprised of a poly (arylene ether) -polysiloxane block copolymer Suggesting a substantial improvement in performance. Corresponding blends made from poly (arylene ether) -polysiloxane graft copolymers exhibited inferior properties.

The description of such specification is intended to be illustrative of the invention, including the best mode, and to enable any person skilled in the art to make and use the invention. The patentable scope of the invention is defined by the claims, and may include other examples that occur to those skilled in the art. Such other examples are intended to be within the scope of the appended claims if they have components that differ from the literal language of the claims, or if they include equivalent components which have non- substantive differences from the literal language of the claims .

All cited patents, patent applications and other documents are incorporated herein by reference in their entirety. However, if the term of this patent application contradicts or conflicts with the term in the integrated document, the term in this application shall supersede the conflicting term in the incorporated document.

All ranges disclosed herein include endpoints, and the endpoints are independently inter-operable.

The use of similar referents in the context of describing the invention (particularly in the context of the following claims) and the articles "a", "an" and "the" It is considered to cover all of the plurality. It should also be noted that the terms "first", "second", etc. herein do not denote any order, amount, or importance, but are used to distinguish one element from another. The modifier "about" used in connection with an amount includes the stated value and has a contextually determined meaning (e.g., it includes the degree of error associated with a particular amount of measurement).

Claims (22)

Based on the total weight of the composition,
55 to 95% by weight of a compatibilized blend of polyamide and poly (arylene ether) -polysiloxane block copolymer; And
1 to 12% by weight of a metal dialkyl phosphinate
Lt; / RTI &gt;
Wherein the poly (arylene ether) -polysiloxane block copolymer is a product of a process comprising oxidation copolymerization of a monomer mixture comprising monovalent phenol and hydroxyaryl-terminated polysiloxane. The method according to claim 1,
The compatibilized blend comprises, based on the total weight of the polyamide and the poly (arylene ether) -polysiloxane block copolymer, 40 to 90 parts by weight of the polyamide and 10 to 60 parts by weight of the poly (arylene ether) - a compatibilized product of a polysiloxane block copolymer. The method according to claim 1,
Wherein the monomer mixture comprises 90 to 99 parts by weight of the monohydric phenol and 1 to 10 parts by weight of the hydroxyaryl-terminated polysiloxane, based on the total weight of the monohydric phenol and the hydroxyaryl-terminated polysiloxane. . The method according to claim 1,
The hydroxyaryl-terminated polysiloxane comprises a plurality of repeating units having the following structure:

Wherein R ⁷ each independently represent hydrogen, C ₁ -C ₁₂ hydrocarbyl or halo-C ₁ -C ₁₂ hydrocarbyl bilim; And
Two terminal units having the structure:

Wherein Y is hydrogen, C ₁ -C ₁₂ hydrocarbyl, C ₁ -C ₁₂ hydrocarbyl, and aryloxy, or halogen, R ⁸ each is independently hydrogen, C ₁ -C ₁₂ hydrocarbyl or C ₁ -C ₁₂ halohydrocarbyl
&Lt; / RTI &gt; The method according to claim 1,
Wherein said monohydric phenol comprises 2,6-dimethylphenol, and said hydroxyaryl-terminated polysiloxane has the structure:

Wherein n is from 5 to 100 on average. 3. The method according to claim 1 or 2,
2 to 40% by weight of glass fibers. 3. The method according to claim 1 or 2,
Wherein the poly (arylene ether) -polysiloxane block copolymer causes 1 to 5% by weight of the polysiloxane to be present in the composition. The method according to claim 1,
75 to 90 weight percent of a commercial blend of polyamide and poly (arylene ether) -polysiloxane block copolymer, and 2 to 10 weight percent metal dialkyl phosphinate;
Further comprising 5 to 15% by weight of glass fibers;
The commercialized blend comprises 40 to 60 parts by weight of the polyamide and 40 to 60 parts by weight of the poly (arylene ether) - polysiloxane block copolymer, based on the total weight of the polyamide and the poly (arylene ether) A commercial product of a polysiloxane block copolymer;
Said polyamide comprising polyamide-6,6;
The poly (arylene ether) -polysiloxane block copolymer comprises 90 to 99 parts by weight of a monohydric phenol and 1 to 10 parts by weight of a hydroxyaryl-terminated phenol, based on the total weight of the monohydric phenol and the hydroxyaryl-terminated polysiloxane, The product of the process comprising oxidation copolymerization of a monomer mixture comprising a polysiloxane;
Wherein the metal dialkyl phosphinate comprises aluminum tris (diethyl phosphinate). An article comprising the composition of claim 1. delete delete delete delete delete delete delete delete delete delete delete delete delete

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